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J. Phys. Chem. Solids, 1973. Vol. 34, pp. 321-335. Pergamon Press.

Printed in Great Britain

NONMETALLIC CRYSTALS WITH H I G H T H E R M A L


CONDUCTIVITY

G. A. SLACK
General Electric Research and Development Center, Schenectady, N.Y. 12301, U.S.A.
(Received 13 January 1972; in revisedform 30 May 1972)

Abstract--Nonmetallic crystals transport heat primarily by phonons at room temperature and below.
There are only a few nonmetallic crystals which can be classed as high thermal conductivity solids,
in the sense of having a thermal conductivity of > 1 W/cmK at 300K. Thermal conductivity measure-
ments on natural and synthetic diamond, cubic BN, BP and AlN confirm that all of them are high
thermal conductivity solids. Studies have been made of the effect on the thermal conductivity of nitro-
gen impurities in diamond, and oxygen impurities in AlN. The nitrogen impurities scatter phonons
mostly from the strain field, the oxygen impurities scatter phonons mostly from the mass defects
caused by aluminum vacancies. Pure A1N as well as pure SiC, BeO, BP and BeS conduct heat almost
as well as does copper at room temperature, while pure natural and synthetic diamonds conduct heat
five times better than copper.
All of the nonmetallic solids that are known to possess high thermal conductivity have either the
diamond-like, boron carbide, or graphite crystal structure. There axe twelve different diamond-like
crystals, a few boron carbide-type crystals, and two graphite structure crystals that have high thermal
conductivity. Analyses of the rock-salt, fluorite, quartz, corundum and other structures show no can-
didates for this class. The four rules for finding crystals with high thermal conductivity are that the
crystal should have (1) low atomic mass, (2) strong bonding, (3) simple crystal structure, and (4) low
anharmonicity. The prime example of such a solid is diamond, which has the highest known thermal
conductivity at 300K.

1. INTRODUCTION A review of the published data shows that


IN 1911 Eucken [ 1] discovered that diamond only a few crystals fall into this category. Most
was a reasonably good conductor of heat at of them are adamantine (diamond-like) com-
room temperature. In 1914 Debye [2] showed pounds such as diamond [2-7], silicon carbide
theoretically why diamond was a good heat [7], silicon[7,8] beryllium oxide[9], and
conductor. In 1951 Berman e t al.[3] showed gallium phosphide[10-13]. The K at 300K
that diamonds at room temperature conduct decreases in this series from 20 W/cmK for
heat even better than copper or silver. Silver diamond to 1 W/cmK for gallium phosphide.
has the highest thermal conductivity of any In all of these crystals the atoms possess
metal at room temperature where its thermal tetrahedral coordination. Let us consider
conductivity, K, is 4.3 W/cmK. For copper what other crystals with the adamantine
the value is 4-0 W]cmK. In metals the heat is structure[14] should have a high thermal
carried primarily by electrons, while in non- conductivity. The binary compounds A1N,
metals at room temperature it is carried pri- AlP, BAs, cubic BN, BP, BeS, and G a N
marily by phonons. We are interested in those may all have K at 300K of greater than
nonmetallic crystals which, like diamond, have I W/cmK. Possible ternary compounds [14-16]
at room temperature a phonon thermal con- with this structure are A12CO, BeSiN2 and
ductivity comparable to or exceeding that of MgSiN2. However, from the compilation given
copper and silver. Those crystals for which by Spitzer[17] it is apparent that ternary
K at room temperature exceeds 1 W/cmK will compounds have lower thermal conductivities
be considered to possess a high thermal than the corresponding binary compounds of
conductivity. the same average atomic mass. Thus the r
321
322 G.A. SLACK

studies in the present work are limited to the 1900K for cubic BN. Thus we expect the
binary adamantine compounds. highest K values at 300K for the adamantine
Another structure with high thermal con- crystals.
ductivity is the a-boron structure [ 18]. Crystals The value of K from equation (1) is strictly
of B~2As2 have a K value of 1.2W/cmK at valid only for face-centered-cubic crystals
room temperature, while a-boron itself is having N = 1 atom per primitive crystallo-
predicted [ 18] to have a K of about 2 W/cmK. graphic unit cell. This means that the phonon
Samples of both graphite and hexagonal boron dispersion curves have only acoustic branches.
nitride are known [ 19, 20] to have high thermal For N/> 2 there will always be three or more
conductivity for heat flow perpendicular to the optic phonon branches. As a general rule
c-axis, i.e. along the tightly-bound sheets. these optic branches have very small group
Graphite[19] has K values up to 20W/cmK velocities, and hence contribute very little
while the highest value for hexagonal boron to K. This is particularly true for large N.
nitride [20] is about 2 W/cmK. For heat flow This means that crystals with large values of
parallel to the c-axis the K is considerably less. N have very low values of K. This type of
behavior was recognized by Eucken and Kuhn
2. PARAMETERS AFFECTING THE MAGNITUDE [33] in 1928. Reviews have been given by
OF K Missenard[34] and Spitzer[17], and recent
The recent theory of the magnitude of K work on this effect has been reported by
for nonmetallic crystals in the temperature Slack e t al. [18, 35]. Thus to find crystals with
range T I> 0, where 0 is the Debye tempera- high K we restrict the candidates to those
ture, has been given by Leibfried and structures with small values of N, the number
Schl6mann [21] and by Julian[22]. In this of atoms per primitive unit cell. Thus crystals
theory like SiO2 and A1203 are not expected to have
high K at 300K. Indeed they do not [36].
K = Bi"V180S/T3, ~ (1) The four rules for finding a nonmetallic
crystal with a high K are:
where B = some constant,/~ = average mass (1) low atomic mass, (2) strong interatomic
of an atom in the crystal, 3s = average volume bonding, (3) simple crystal structure, and
occupied by one atom of the crystal, and y = (4) low anharmonicity. Conditions (1) and
Griineisen's constant. The factor /~03 is (2) mean a high 0, condition (3) means low N,
maximized for light mass, strongly bonded and condition (4) means small 7.
crystals like diamond because the 03 term
dominates the behavior. The 3,2term is smallest
for adamantine crystals like Ge, Si and 3. ADAMANTINE COMPOUNDS STUDIED
diamond. The high temperature values of 3, In order to test the assumption that the
are 0.73, 0.45 and 1-3 for these three crystals adamantine compounds in general have high
respectively [23-26]. No other crystal struc- K values, measurements of K were made on
tures consistently have such small values the following crystals: Diamond, cubic BN,
of y. The alkali halides LiH, LiF and NaF, BP, AIN and BeO. The BeO results have
for example, have high temperature 3" values recently been published [9]. The other samples
of 1.4, 1.6 and 1-5, respectively [27-29]. Most of adamantine compounds studied are listed
crystals have 1 ~<3" ~< 2, while the soft rare gas in Tables l(a) and l(b). Both single crystal
crystals like argon[30] have 3"= 2.7. The and polycrystalline ceramic samples were
adamantine structure also possesses the used. The samples were generally in the
highest Debye temperatures known. These shape of rods with a rectangular, nearly-square,
are[31,32] 0=2240K for diamond and cross-section. The length of the rod is l and the
N O N M E T A L L I C CRYSTALS 323

Table 1(a). Some adamantine samples for thermal conductivity studies


Size, mm Type Impurities
Sample Run No. I d [a] Source Color [e]

Diamond R201 5.0 3'8 SSC G E (b) Colorless 1'5 x 10~a/cm3-N


Diamond R207 4.9 1-1 SSC G E (b) Colorless 9 10JS/cm3-N
Diamond R208 5.1 1-1 NSC Light yellow 3.5 x 102/cma-N
bands
Cubic BN R189 7.7 2.5 HP G E (c) Grey ceramic 1% binder
Cubic BN R190 5-7 2.6 HP G E (c) Grey ceramic ~< 2 x 10~91cm3-O,C
BP R 151 1.8 1.0 SSC G E (d) Light grey,
transparent

[a]SSC = synthetic single crystal


NSC = natural single crystal
HP = hot pressed polycrystalline ceramic
[b]Grown by H. M. Strong and R. H. Wentorf Jr. of this laboratory, see Ref. [37]. Sample R207 was
a [ 100] axis rod.
[c]Prepared by H. P. Bovenkerk, General Electric Speciality Materials Dept., Worthington, Ohio.
The particle size was about 2 x 10-acm and the sample density was 97 per cent of theoretical. Sample
R 189 contained an oxide binder, sample R 190 contained no binder.
[d]Grown by F. H . Horn of this laboratory, see Ref.[18].
[e]The nitrogen in the SSC diamonds all occurs as dispersed nitrogen. The nitrogen in the NSC, R208
diamond occurs as platelet nitrogen, the dispersed nitrogen content is < 2 x 10tr/cm"~.The impurity content
of the BP is unknown, see Ref. [ 18] for comments.

Table 1(b). A IN samples for thermal conductivity studies


Size, mm Type c0[f] Totaloxygen[g] Kat300K
Run# / d [a] Source Color 10-Scm 10~atoms/cc W/cmK

R162 8.0 1.5 SSC Pechiney[b] Blue-grey 4.9809 3-----2 2-0


R 169 6.3 1"2 SSC Pechiney [b] 4.9806 3-- 2 2.0
R163 11-8 3.0 HP G.E. [c] Blue-grey 4.9789 11 -----2 0-28
R 174 11 "5 5.0 HP G.E. [c] Light-grey 4-9796 11 --- 2 0.65
R191 11"8 3.2 CPS NIRIM[d] Chalkwhite 4.9810 ~< 12 0.145
R196 9.5 2-3 HP G.E. [c] Steel grey 4.9788 43 +__2 0.41
R211 21"0 3-5 HP Cerac[e] Grey 4.9780 22-1 0-60
R212 12-7 3"3 HP G.E.[c] Chalk grey 4.9801 47---4 0.44
R213 11-0 2.7 HP G.E. [c] Grey 4.9793 11 1 0.74

[a]SSC = synthetic single crystal


HP = hot pressed polycrystalline ceramic
CPS = cold pressed and sintered ceramic
[b]Grown by sublimation at about 2100C in a commercial production furnace. Obtained from the
Pechiney Compagnie de Produits Chimiques et Electromrtallurgiques, Grenoble France with the
help of Dr. E. C. Lightowlers, University of London, see U.S. Patent 2,962,359 (1960). The crystals
were transparent with a blue-grey cast and had several brown streaks running through them. For
sample R 162 the crystallographic c-axis was tilted 62 away from the axis of the rod.
[c]Hot pressed in this laboratory at 1900"C and 300 atmospheres. The density was greater than
97 per cent of the theoretical density of 3.26 gm/cm a.
[d]Obtained from Dr. M. Iwata, National Institute for Researches in Inorganic Materials, Tokyo,
Japan. The sample had been cold pressed and sintered, the density was 62 per cent of theoretical.
[e]Obtalned from Cerac Hot-Pressing Inc., Menomonee Falls, Wis. The density was 94 per cent
of theoretical.
[f]Generally accurate to 5 x 10-12 cm.
[g]Measured using neutron activation techniques by Gulf Energy and Environmental Systems,
San Diego, California.
324 G.A. SLACK

diameter, d, is the diameter of a circle of repeated with 0.0025 cm dia. wire because
equal cross-sectional area. the only available crystal was quite small.
The synthetic diamonds were grown as The K values are believed to be accurate to
large, single crystals[37] in a high tempera- ___5 per cent except for BP, where the accuracy
ture, high pressure apparatus. The cubic is probably ___10 per cent.
BN [38] was synthesized in a similar apparatus.
The BP was grown from liquid palladium [18]. 5. RESULTS
The value of K is sensitive to the impurity (a) D i a m o n d
content of the samples, particularly those The K vs temperature curve for diamond is
impurities that enter as substitutional atoms given in Fig. 1. The K for the two synthetic
in the lattice. For diamond the commonly diamonds is shown to be larger than the best
troublesome impurity is nitrogen[6]. The
nitrogen content in samples R201, R207 and I I I I I
R201..-,~,:~
R208 was determined by measuring the opti- 0,AMON0
cal absorption coefficient at 480 or 1130 cm -1. 102 - R20 , --
In the synthetic crystals this occurs as dis-
persed nitrogen, in the natural crystals it
occurs mostly as 'platelet' nitrogen[39]. A
study of R208 by electron paramagnetic ~ IO -
resonance [40] placed the content of dispersed R 208
nitrogen in this natural crystal at < 2 x 1016/
cmz. In either case, platelet, or dispersed, the
nitrogen reduces the K of diamond.
In aluminum nitride, AIN, the common ~ I0C

troublesome impurities are carbon, oxygen,


and silicon. Mixed crystals of A1N can be
made with A14C3141, 42], A12Os[43], AI2OC
[44, 45], SiC [46] and probably SisN4. At low
concentrations the wurtzite crystal structure /
of AIN is retained. For the samples of AIN
in Table 1 the dominant impurity was oxygen. /
Apparently[43] the oxygen content in the I I I I I
10-2 3 IO 30 I00 300 I000
absence of carbon can be as large as 1.5 1022 TEMPERATURE, K
atoms/cm z. The oxygen content of the samples Fig. ]. T h e thermal conductivity o f two synthetic and one
was analyzed by neutron activation analysis natural diamond vs temperature. Two of Berman's curves
[47]. for types Ila and 1 natural diamonds are shown.
An upper bound is given to the impurities
in the BN. No information about impurities natural crystal of a Type IIa diamond
in the BP is available, see however Ref. [ 18]. measured by Berman et al. [5]. The maximum
K for R201 was Kmax= 175 W/cmK at 65K.
4. EXPERIMENTAL TECHNIQUE Sample R207 had a maximum of K = 140
The thermal conductivity was measured W/cmK at 70K. In Table 2 values are given
with an apparatus [48] described previously. for what is believed to be the intrinsic thermal
For all of the samples the temperatures were conductivity of diamond from 100 to 300K
measured with gold-cobalt versus manganin based on sample R201.
thermocouples of 0.0076cmdia. wire. For The natural crystal R208 was chosen to
the BP sample the measurements were have as large a concentration of nitrogen as
N O N M E T A L L I C CRYSTALS 325

Table 2. The intrinsic thermal conductivity of found by Eucken [ 1] for diamond is probably
pure diamond, BP, SiC and LiH in error. He did not have his thermometers
attached directly to the diamond, and was
Thermal conductivity troubled by thermal contact resistance.
Temp. Diamond BP SiC LiH
The platelet nitrogen in natural diamonds
50 52 3-6 was shown by Kaiser and Bond[49] to be
70 43 1"75 nitrogen atoms substitutionally incorporated
100 130 > 14 28 0-93
150 65 10.0 15 0.46
for carbon. The nitrogen atoms do not pre-
200 40 6-5 9-5 0-29 cipitate as large (i.e. > 100 ~ dia.) size, second
250 27 4.6 6.5 0-20 phase inclusions. If they did, their effect on
300 20 3'5 4.9 0.147
500 8.0 [a] 2-2 0.067 K would be very small, contrary to the results
700 4.5 [a] 1.30 0.041 in Fig. 4.
1000 2.5 [a] 0.76 0.027 [b] The observations that the synthetic dia-
1300 0.50
1700 0.33 monds, because of their low nitrogen content,
have as high or higher thermal conductivity
[a]Estimated value. than the best natural samples makes them
[b]Extrapolated to melting point of 961 K. attractive for heat-sinking [52-56] semi-
conductor devices. A nitrogen content of
could be found in a good crystal, which was 1019/cm3, see Table 1A, decreases the K at
3.5 10~/cm3. Natural diamonds with con- 300K to about 18 W/cmK from a value of 20
centrations up to 4.2 102/cm3 have been W/cm K for pure diamond. This effect in syn-
reported[49, 50]. Crystal R208 has a maxi- thetic diamonds would be small for most
mum of K = 19 W/cmK at 85K and K = 6-8 practical applications.
W/cmK at 300K. The K vs T curve for this
sample with 3.5 102atom/cm3 of nitrogen (b) Boron nitride
is slightly lower than Berman's[5] sample No crystals of synthetic [38], cubic BN were
with 1-7 102atom/cm3 of nitrogen. The available that were large enough to measure
higher nitrogen content produces a lower K. Hence the measurements were made on
K. If the added thermal resistivity, AW, at polycrystalline ceramic compacts that had
300K produced by the nitrogen is proportional been made at high temperatures and pressures.
to the nitrogen concentration, An, then one The samples had a density of 97 per cent of
obtains theoretical, and a grain size of 2 x 10-3 cm. The
results are shown in Fig. 2. The K of R190, a
(AW/An) = 0.31 10-21 cm4K/W self-bonded compact, is higher that that of
R189 which contains some oxide binder
for the factor of proportionality. If one cal- between the grains. The K of R190 at 300K
culates W(no/An)_, where no is the number of is 1.8 W/cm deg. Hence it is concluded that
carbon atoms per unit volume in diamond, pure, single crystal cubic BN will have K > 2
i.e. no = 8-3, then W/cmk at 300K. How much greater is un-
certain, but the considerations in Section 7
AW(no/An) = 55 cmK/W (2) put this value at about 13 W/cmK. Thus one
might expect to see a considerable increase
If 4.2 10Z/cm3 is the maximum nitrogen in the K of cubic BN compacts as the bonding
concentration in diamond, then K I> 5-5 W/cm between the grains improves and the oxygen
K at 300K for any diamond. The result is in and carbon content within the grains decreases.
agreement with the results of Schorr [51]. The estimated K of BN derived from K
This means that the low K value of 1.7 W/cmK measurements on gas-solid mixtures by
326 G.A. SLACK

102
ioo
CUBIC BN

RI9
10I
IO"l
_>

z i-
8
>

w
~ 10o

io-2

u.I
-r
~- 10-1

I [ I I I
10-3 3 I0 30 I00 300 IO00
TEMPERATURE, K

Fig. 2. The thermal conductivity of polycrystalline cubic 10-2


BN vs temperature. The curve of Lezhenin et al. is an I 3 IO 30 I00 300 I000
estimate. TEMPERATURE, K

Fig. 3. The thermal conductivity for single crystals of a


number of adamantine compounds vs temperature.
Lezhenin et al.[57] is also shown in Fig. 2.
T h e true K of pure, cubic BN is probably much
higher. [7] from 3 to 300K. At that time an attempt
was made to extrapolate these results to T =
(c) Boron phosphide 0. Since then more data [59-61] have b e c o m e
The K vs T curve for a single crystal of BP available, and the previous extrapolated values
is shown in Fig. 3. This sample has a maxi- appear to be too large. Based on all the avail-
mum of r = 1 4 W / c m K at 80K. The results able information, the best current estimates of
from 50 to 300K indicate that the K of BP is the K of pure SiC are given in Table 2. T h e K
very close to that of BeO [9] in this tempera- of SiC at T = 0 = 1080K is now believed to
ture range. T h e intrinsic r values based on be 0 . 6 7 W / c m K . This new extrapolation is
these data are given in Table 2. T h e r vs T also shown in Fig. 3. In this extrapolation K
curve in Fig. 3 is representative of a crystal varies as T -1'5s for the range 200K ~< T ~<
with probably less than 1019/cm 3 of impurities. 1700K. This curve thus resembles the results
H o w e v e r , very little is known about the for BeO [9] for T > 200K, also shown in Fig. 3.
possible impurities in these samples. T h e
results of Post[58] on BP ceramics from 475 (e) Aluminum nitride
to 865K show K values a factor of 6 lower than T h e present K results for AIN are shown
would be expected, presumably due to impuri- in Fig. 4 together with published data from
ties in his material. the literature [44, 62-64]. T h e literature results
for A1N, all for T 1> 300K, show considerable
(d) Silicon carbide variability, somewhat similar to the literature
T h e thermal conductivity of moderately results [7] for Si and SiC. T h e major factor
pure SiC single crystals has been measured in producing this scatter in Fig. 4 appears to
N O N M E T A L L I C CRYSTALS 327

I01 , i \ , i , 7B and the results in Fig. 4. Oxygen is the most


AtN \~PPERLIMIT common impurity in the samples studied [44,
62], but carbon was also a problem [44, 63].
R I 6 Z ~ \
~/~,~ \ TAYLO8R (i) Oxygen impurities. For the samples listed
~ 10o
CRYSTALS- ~
,,o, R174 \\ LENIE/ in Table l(b) the dominant impurity was
RI96 \ oxygen. Some care had been taken to eliminate
carbon, silicon, iron and other impurities. The
~ 10-1
oxygen enters the AIN lattice and substitutes
for the nitrogen up to very high oxygen
.ff concentrations [43]. In-this process one mole-
ANDREEVA
CE /o/ et ol.
~/ oL ONG8 cule of A10.670 substitutes for one molecule of
io-~
FOSTER A1N. Since the tetrahedral covalent radius of
oxygen is less than that of nitrogen[65], and
since metal vacancies occur on the aluminum
sites, the AIN lattice parameter should
io- I
Io t~o 36o ,oGo ,o,ooo decrease as the oxygen content increases.
TEMPERATURE, K This has been verified experimentally in
Fig. 4. The thermal conductivity of both single crystal Fig. 5 where the c-axis lattice parameter
(R162 and R169) and ceramic samples (others) of AIN determined from X-ray powder patterns has
vs temperature. The upper limit curve for pure AIN is been plotted vs the oxygen content deter-
an estimate based on the results shown in Fig. 3.
mined from neutron activation. All of the
points plotted in Fig. 5 were taken on samples
be the variable chemical purity and density that had been equilibrated at about 2000C in
of the AIN samples. an inert atmosphere or vacuum. Sample R196
The density of some of the samples studied is known to have a small amount of some
[62, 64] was only about 65 per cent of theore- second phase in it from the X-ray results. This
tical, and can account for low K values. See phase contains oxygen, but has not yet been
also the comments on sample R191 in Table identified [66]. From Fig. 5 it appears that the

4.98]
=-b~4.98C ~ R 174 MN
R2~St-~ ' I
Z
"~~?1.~1 RI96
~ 4.975
m
x

i I i I I I i I
4.97C
I0 20 30 40
OXYGENCONCENTRATION,102ocm-3

Fig. 5. The c-axis lattice parameter of AIN as a function of the oxygen concentration. Sample
R196 has two phases in it.
328 G.A. SLACK

maximum solid-solubility of oxygen at about replaced by oxygen, Co= c-axis lattice para-
2000C is 2 x 1021/cms. For some AIN + Al2Os meter of pure A1N, Ac = change in c-axis
samples made in this laboratory at 100(2 the lattice parameter caused by An. A study of
smallest c-axis lattice constant found was the co[ao ratio of various A1N samples doped
4.9685 .A, which corresponds to about 6 x 1021/ with Al0.oTO shows that this ratio remains
cm s of oxygen. This concentration is 1/3 of essentially constant at co/ao = 1.6004. Thus
the maximum reported previously [43] of 1.5 the introduction of Alo.070 produces a volume
102~/cms. This lattice constant is similar to that contraction of the A1N, and at 100% Al0.nTO
found by Kohn et al.[67] for AIN crystals the volume would be 6.3 per cent less than that
grown in the presence of air, see Table 3. The of A1N. This crystal structure would have

Table 3. Lattice parameter of A I N

Lattice parameter, 10 -s cm
Co ao Author Year Ref.

4.991 3" 119 Ott 1924 68


4.975 __.0.008 3" 110 ___0.005 yon Stakelberg and Spiess 1933 41
4.965__+0.01 3-100.01 Kohnetal. 1956 67
4.978 3" 111 Jeffi'ey et al. 1956 69
4.980 3.111 T a y l o r and Lenie 1960 44
4.982___0.003 3.1110.003 Drum 1965 70
4.9816 0.0005 3" 1127 0.0003 Present work [a] 1971 --

/a/Calculated density is 3.255 g/cm a.

range of lattice parameters found [41,44, 67- tetrahedral AI-O bonds 1.86/~ long, which
70] for A1N is given in Table 3. The very high would be somewhat larger than the value of
value found by Ott[68] is probably caused 1.82 ,~ found [71] in the tetrahedral structure
by about 10 mole% of AI2OC in his crystals, A1404C. Hence the hypothetical wurtzite
since they were made in a carbonaceous structure for A10.670 is only stable at lower
atmosphere. Taylor and Lenie also found oxygen concentration where it forms mixed
[44] an increase in lattice parameter when crystals with AIN.
A12OC was incorporated. These results are (ii) Thermal conductivity. Now that the
understandable since the lattice parameters oxygen solubility in AIN is established, we
[45] of A12OC are about 2 per cent larger can begin to understand the K results in Fig. 4.
than those of A1N. The other samples shown Let us consider K at 300K. Since K decreases
in Table 3 have lattice parameters less than with increasing impurity concentration, the
Co = 4.9816 A a0 = 3.1127 ,~, (co/ao = 1.6004). thermal resistivity, W = K-I, is a more useful
This is caused by the incorporation of Alo.670 quantity. In Fig. 6 a plot of W vs oxygen con-
into the lattice. The crystals studied by Kohn centration is shown for several AIN samples.
et al. [67] were the most heavily contaminated. Samples R169, R213, R174 and R211 are all
The results in Fig. 5 show that single phase ceramics, and the oxygen is in
solid solution in the AIN, as shown in Fig. 5.
AC/Co = - 0"021 (An~no) (3) In samples R212, R196 and R163 the oxygen
content is too large for the A1N and some
where no number of nitrogen atoms per cm s
= oxygen occurs in a second phase. The long
in pure AIN = 4.79 x 1022/cma, An = the horizontal bars for these three samples in Fig.
number of nitrogen atoms that have been 6 extend from the oxygen concentration in
N O N M E T A L L I C CRYSTALS 329

, i , i
' ' I RI63 I I I I I I

3
300K

:
E
IRI96
qR212

A/N

/
Q: 3001(
R215
6

4 BP&~BeO
RI69

OXY(~r.N CONCENTRATION, 1020cm "3

Fig. 6. The thermal conductivity at 300K of AIN samples


as a function of the oxygen concentration. The heavy, I
solid line extrapolates to r = 3'2 W/cmK for pure AIN.
0.~ t I I I I I
2 4 6 8 10 20 30
the AIN, as determined from the A1N lattice M~ 03/100, ~ cmK3
parameter in Table l(b), up to the total oxygen Fig. 7. The thermal conductivity at 300K of various
content in both phases, as determined by the adamantine compounds vs the scaling parameter. The
neutron activation. The results in Fig. 6 can arrows on the experimental points for AIN and cubic
BN indicates that the expected values for pure single
be fitted by the heavy solid line which starts crystals lie on the line directly above. See Table 5.
at pure AIN where W0 = (1/3.2) cmK/W, see
Section 7. The incremental thermal resis-
impurity limit for commonly occurring
tivity caused by the oxygen is AW = W-- W0.
impurities is -- 5 x 102/cma.
The slope of the line in Fig. 6 is:
6. ANALYSIS OF RESULTS
(AW/An) = 0.90 x 10-21 cm4K/W.
It would be very tedious to generate
computer fitted K VS T curves for all of the
Then if no is the number of nitrogen atoms
samples in Figs. 1-4. Hence a simpler
per cm 3 in AIN, the results for Alo.erO in
approach will be taken. A computer fit for
A1N is:
silicon and for a diamond sample similar to
(AWno/An) = 43 cmK/W. (4) R208 in Fig. 1 has been carded out by
Agrawal and Verma[72], and they conclude
This is quite similar to the value found in that the point impurity scattering in diamond is
equation (2) for nitrogen in diamonds. much higher than predicted by the carbon iso-
So the thermal resistivity produced by topes. It is clear, now, that nitrogen impurities
A10.670 impurities in AIN can explain the large are responsible. At temperatures below 4K the
range of K values in Fig. 7. The magnitude of Kof diamond is well explained [72] by boundary
the effect will be shown in Section 6 to be scattering. Similarly in Fig. 3 the K at 2K of all
about right. The reason that the K of tklN at of the samples except the BP (R151) is
300K can sometimes be so low is that the explained by boundary scattering. Some
starting powder from which the sample is made impurity scattering probably exists in the BP
can contain up to 1.5 x 1022/cms of oxygen. In sample for T < 100K. The Kat room tempera-
most of the other adamantine compounds this ture (and above) of the pure crystals will
330 G.A. SLACK

be treated comprehensively in Section 7. The A1N:


main feature of present concern is the W = 238 I" A cmK/W. (9)
explanation of the magnitude of the impurity
effect on K. For low concentrations of A10.670:
Impurity effects are important in AIN and
diamond, see equations (2) and (4). The effect x(1--x) = x = An/no.
of substitutional impurities on the K of
adamantine compounds has been treated by Thus the calculated value is
Abeles[73] for the temperature range T~>
0. He considers that a substitutional impurity (AWno/An) = 74 cmK/W (10)
produces both a local mass difference, AM,
and a local lattice mismatch, Aa, in the lattice. for the temperature range T/> 0. The experi-
In his treatment he considers the parameter mental value at T = 0.32 0 is given in equation
gamma: (4). The agreement is good considering the

= x,xI4 + 40 (5)
assumptions involved. Thus the major source
of the phonon scattering in AIN produced by
A10.670 impurity is the mass difference of the
A1 vacancies.
where x is the fraction of lattice sites occupied
For nitrogen in diamond Agrawal and
by the impurity, and the subscript A means
Verma[72] have shown that if the point
Abeles. The quantity Fa is 12 times larger
impurity scattering relaxation time, %, is
than the customary[48, 74] definition of F.
given by
Hence:
tp-a = Ao9 4,
r = (FA/12) (6)
where ~o is the phonon frequency in rad/sec,
For substitutional A1o.670 impurities in AIN then
one molecule of Alo.670 is assumed to produce A = 2.09 x 10-4's sec 3
a small mass change in the nitrogen lattice,
i.e. 16 vs 14, and a larger mass change in the for Berman's sample with 1-7x 102/cm3 of
AI lattice by creating 1/3 of a vacant lattice nitrogen. This value of A corresponds [73] to
site. The method of calculating F when two
sublattices are involved has been outlined Fa = 3"65 x 103.
previously[74]. Thus for one molecule of
Al0.s70 in AIN: Since the mass difference between carbon and
nitrogen is small, the calculated value of l'a
from equation (5) assuming A6 = 0 is
-~-M)2 = 0.289 + 0-005, (7)
Fa = 2"8 10-s
where the first term on the right is for the AI
lattice and the second is for the nitrogen or too small by a factor of 140. Clearly Aa > 0
lattice. The (AS/a) term in equation (5) is for nitrogen in diamond, and most of the
2.1 x 10-z from equation (3). The result is: phonon scattering produced by the nitrogen
is caused by the strain field of the lattice
FA = 0"310x(1--x). (8) mismatch and not by the mass difference.
Equation (5) would require:
If a reasonable value of a = 2.5 is assumed
for a in equation (25) of Abeles [73], then for (Aala) = 0.3
NONMETALLIC CRYSTALS 331

to account for the observed effect of nitrogen. [81] and a guess as to the probable extra-
This value of A8 appears to be too large from polation of the 0 vs T curve to absolute zero.
the work of Kaiser and Bond [49] who find: The 0 for G a N was calculated using the
approach of Steigmeier[32] and the known
(A8/8) = 0.053. 0 values of BeO and AIN. In Fig. 7 K has been
plotted versus this scaling parameter. The
So the situation for nitrogen in diamond is agreement is good except for A1N and BN
not clear, but the phonon scattering cross- where the observed K falls much below the
section is clearly larger than that due solely line. F o r these crystals the r is probably
to the mass difference between nitrogen and limited by impurities, and hence is lower
carbon. than the intrinsic K. In fact the extrapolated
r for pure A1N at 300K from Fig. 6 is 3.2
7. SCALING P A R A M E T E R S FOR K AT 300K w/cmK, in agreement with the expected value
From the present measurements on from Fig. 7. F o r pure, cubic BN the expected
diamond, cubic BN, BP, and A1N it is clear K at 300K from Fig. 7 is 13 W/cmK. F r o m
that the pure crystals all qualify as high K Table 4 and Fig. 7 it is possible to make
solids. F r o m equation (1) we take the expres- estimates of the K to be expected for the
sion A~803 as a convenient scaling parameter crystals BeS, BAs, G a N and AlP for which
for the adamantine compounds at a fixed T no data exist. T h e s e estimates are given in
of 300K. The Grfineisen parameter 7 has Table 5 together with the known K values for
been omitted, since it is not known for all of the other crystals. A table similar to Table
the crystals. In Table 4 this scaling parameter 5 has been made by Steigmeier[82] for other
has been calculated for all of the adamantine adamantine crystals where K < 1 W / c m K at
crystals that have high K. T h e literature Ref. 300K. F r o m Table 5 it is predicted that there
[7, 9, 3 1 , 3 2 , 75-80] for 0 and K are also given are twelve adamantine crystals that can be
in Table 4. T h e 0 for SiC was computed classed as high K nonmetals. O f these dia-
from estimated elastic constants [76, 77]. mond has the highest K, and cubic BN is a
The 0 for BeS was estimated from a com- close second. Measurements on high purity
parison[78, 79] with BeO. The 0 for A1N was single crystals of several o f the others are
calculated from the measured heat capacity needed to confirm these predictions.

Table 4. The scaling parameter ffl~O3for adamantine compounds


with high thermal conductivity [a]
lffl 28 0 ff18031100 Reference
for
Crystal g 10-a cm K gcm Ka r 0
Diamond 12.01 3.56 2240 23"8 3-6, P 31
Silicon 28.09 5.43 645 2'05 8 75
BN(cubic) 12.41 3.62 1900 15"4 P 32
SiC 20-05 4.36 1080 5"5 7, 59-61 7, 76.77
BeS 20-54 4.85 900 3"63 -- 78.79
BP 20.89 4"54 985 4"53 P 32
AlP 28.98 5.45 588 1-60 -- 32
BAs 42.87 4-78 625 2"50 -- 32
GaP 50.34 5-45 445 1"21 10-13 80
BeO 12-51 3.81 1280 5.00 9 9
AIN 20-49 4.37 950 3"84 P 81
GaN 41.86 4.49 600 2"03 -- 32

[a]P = present work, 28 = the lattice constant for the cubic crystals.
332 G.A. SLACK

8. LITHIUM HYDRIDE y = 1.4, for most of the adamantine compounds


The compound LiH has an average y ~-0.7. Hence we expect, from equation (1)
atomic mass M = 3.97 g, a Debye temperature the K of LiH to be lower by a factor of (1-4/
0 = 1070K as calculated from the elastic 0.7) z = 4. Thus even the rocksalt compound
constants[27], and a simple crystal structure with the l o w e s t / ~ and highest 0 is too anhar-
(NaC1 type) with N = 2. It has a value for monic, i.e. has too large a phonon-phonon
M603 of scattering, to classify as a high K crystal. In
Fig. 8 the K curves for LiF [90-92] and N a F
M803/100 = 0.993 g cm K 3. [93, 94] are shown for comparison with LiH.
At 300K and above the K of LiF is slightly
From Fig. 7 we might expect LiH to have lower and that of N a F is slightly higher than
K - 0.8W/cmK at 300K. Measurements of that of LiH. The scaling parameters [95-97]
K have been made[83-89] for LiH, and are are also similar. This means that the K of
shown in Fig. 8. See also Table 2. The experi- LiH behaves like the r of the alkali halides.
mental value of r is K = 0"15 W/cmK at 300K. A survey of the r of other rocksalt structure
This is lower than predicted by a factor of compounds indicates that none[33, 74, 98,
5-3. This difference between LiH and the 99] of them can be classed as a high K Crystal.
adamantine crystals can be attributed.mainly
to the difference in y. For LiH we have[27] 9. CONCLUSIONS
(1) High purity synthetic diamonds have K
values somewhat greater than the best
natural diamonds so far studied. The K of
103 diamond is sensitive to the nitrogen content,
and at 300K varies from 20 W/cmK in pure
diamond to about 5.5 W/cmK for the most
heavily doped crystals. The phonon scattering
is probably caused by the strain field around
the nitrogen impurities.
(2) The r of A1N is sensitive to the oxygen
content, and at 300K varies from about 3.2
W/cmK in pure AIN to about 0-5 W/cmK for
2 1021/cm3 of oxygen. Even lower K values
can occur at higher oxygen contents or in
two-phase ceramics. The phonon scattering
in the oxygen doped samples appears to be
caused by the mass defect of the aluminum
ItV its0 I--
vacancies as A10.6~O is dissolved in the AIN.
(3) In order for a nonmetallic crystal to pos-
sess high thermal conductivity it must have
LiH
VETRANO low average atomic mass, strong interatomic
+ FIELDHOUSEet ol.
MAM~ING8 McKEE bonding, a simple crystal structure, and low
o THACHER
anharmonicity.
(4) There are twelve adamantine crystals
I I
DO
t
300
I
1000 with high thermal conductivity. This means r
TEMPERATURE,K values ~> 1 W/cmK at 300K. These range
Fig. 8. T h e thermal conductivity o f L i H , L i F and N a F from diamond to gallium phosphide, and are
vs temperature as reported in the literature. listed in Table 5. Their K values at 300K are
N O N M E T A L L I C CRYSTALS 333

T a b l e 5. T h e r m a l c o n d u c t i v i t y at 3 0 0 K o f a d a m a n t i n e
c o m p o u n d s . T h e v a l u e s in p a r e n t h e s e s are e s t i m a t e s f r o m
Fig. 7

K K K
Crystal W/cmK Crystal W/cmK Crystal W/cmK
Diamond 20 BP 3.6 GaN (1"7)
BN(cubic) (13) A1N (3"2) Si 1.6
SiC 4-9 BeS (3"0) AlP (1"3)
BeO 3"7 BAs (2"1) GaP 1-0

proportional to the scaling parameter .~t~0a, Phys. Chem. 75, 1838 (1971). The lowest curve for
see equation (1). diamond in Fig. 9 of this paper is actually for sample
R208. It was inadvertently attributed to Berrnan.
(5) Several other crystals with the a-boron, 8. G L A S S B R E N N E R C. J. and SLACK G. A., Phys.
boron carbide, or graphite structures also Rev. 134, A1058 (1964).
possess high K values. 9. SLACK G. A. and A U S T E R M A N S. B., J. appl.
Phys. 42, 4713 (1971).
(6) There are no crystals with the rocksalt 10. WEISS H.,Ann. Phys. 4, 121 (1959).
structure, not even LiH, that possess high 11. W A G I N I H., Z. Naturf A21, 2096 (1966).
thermal conductivity. This is caused primarily 12. S T E I G M E I E R E. F. and K U D M A N I., Phys.
Rev. 141, 767 (1966).
by lower 0 and higher T values in these 13. M U Z H D A B A V. M., N A S H E L S K I I A. Ya~,
compounds compared to the adamantine T A M A R I N P. V., and S H A L Y T S. S., Fiz. tverd.
Tela 10, 2866 (1968) [English Trans. Soviet Phys,
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14. W Y C K O F F R. W. G., Crystal Structures, Vols. 1
Acknowledgements--I would like to thank J. H. and 2, Second Edition, Interseienee, New York
McTaggart and W. S. Knapp for their help in making (1963).
the thermal conductivity measurements. Thanks are also 15. E C K E R L I N P., R A B E N A U A. and N O R T M A N N
extended to F. H. Horn for the BP crystal, H. M. Strong H., Z. Anorg. Allgem. Chem. 353, 113 (I967),
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20. STUCKES A. D., private communication.
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